Marking material for high-pollution-resistance photovoltaic solar panel and preparation method of marking material

Abstract

The invention relates to a high-pollution-resistance identification material for a photovoltaic solar panel and a preparation method of the high-pollution-resistance identification material. A high-pollution-resistance photovoltaic solar panel identification material is composed of a polyester film PMMA (the mechanical strength is enhanced through polycarbonate diol modification) and environment-friendly release paper, the polyester film PMMA and the environment-friendly release paper are bonded through a terpene resin-based cementing agent, the cementing agent adopts modified terpene resin as a core, and wear-resistant PAA resin, an oily anti-aging agent, a flatting agent, a silicon defoaming agent, a photoinitiator, ethyl ester and a water repellent agent are used as auxiliary materials. The pollution resistance is enhanced. The modified terpene resin is prepared through a tetrafluoroethylene grafting reaction under nitrogen, and the weather resistance and the chemical stability are improved. The invention relates to a preparation method of a high-pollution-resistance photovoltaic solar panel identification material. The preparation method comprises the following steps: preparing a terpene resin-based cementing agent, and coating and laminating. The material is excellent in performance in outdoor severe environments, resistant to pollution and damage and capable of guaranteeing long-term stable operation of a photovoltaic system.

Description

Technical Field

[0001] The present application relates to the technical field of identification materials, and in particular to an identification material for photovoltaic solar panels with high anti-fouling properties and a preparation method thereof. Background Art

[0002] With the global pursuit of clean energy and sustainable development, photovoltaic solar panels, as a clean, renewable energy technology, have been widely used and received attention. In photovoltaic power stations and distributed photovoltaic systems, in order to ensure the normal operation of the system, improve safety and management efficiency, it is particularly important to mark photovoltaic solar panels. Through marking, the type, specification, installation location and other information of photovoltaic solar panels can be clearly identified, which facilitates the maintenance, inspection and management of the system.

[0003] Photovoltaic solar panels are usually installed in outdoor environments and are exposed to natural conditions such as wind, sun, rain and snow for a long time. They are easily corroded and attached by various pollutants. Therefore, the marking material needs to have excellent anti-fouling performance and be able to remain clearly visible for a long time. The service life of photovoltaic solar panels is usually long, so the marking material also needs to have corresponding durability and permanence to maintain the clarity and integrity of the marking for a long time.

[0004] The anti-fouling marking materials currently on the market generally have the problem of poor anti-fouling performance, especially for paint, ink and acid-base substances, which are very difficult to clean. In addition, the existing anti-fouling marking materials are cumbersome to use and usually need to be directly applied to the carrier or the marking surface, which is not only time-consuming and labor-intensive, but also difficult to achieve the ideal anti-fouling effect. Therefore, it is particularly important to develop a photovoltaic solar panel marking material with high anti-fouling performance and easy to use and a preparation method thereof. Summary of the invention

[0005] The present application provides a highly anti-fouling identification material for photovoltaic solar panels and a preparation method thereof, which aims to solve the problems of poor anti-fouling performance, insufficient durability and cumbersome usage of existing identification materials on the market, and provides a strong guarantee for the normal operation, maintenance and management of photovoltaic power stations and distributed photovoltaic systems.

[0006] In the first aspect, the present application provides a highly anti-fouling photovoltaic solar panel identification material using the following technical solution: a highly anti-fouling photovoltaic solar panel identification material, comprising a polyester film PMMA and an environmentally friendly isolation paper, wherein the polyester film PMMA is bonded to the environmentally friendly isolation paper via a terpene resin-based binder; The raw materials for preparing the terpene resin-based binder include the following components by weight percentage: Modified terpene resin 32-36% Wear-resistant oily PAA resin 10-12% The preparation method of the modified terpene resin comprises the following steps: S1. Dispersing the terpene resin in a mixed solution of chloroform and acetone, and then adding tetrafluoroethylene monomer and benzoyl peroxide to the mixed solution under a nitrogen atmosphere, and mixing them evenly; S2. Control the reaction temperature to 25-50 degrees Celsius. After reacting for 5-15 minutes, the tetrafluoroethylene monomer is grafted onto the main chain of the terpene resin under the action of benzoyl peroxide to obtain a modified terpene resin.

[0007] By adopting the above technical solution: a highly anti-fouling, durable and easy-to-use identification material for photovoltaic solar panels has been successfully developed, providing strong support for the maintenance and management of photovoltaic power stations and distributed photovoltaic systems.

[0008] Analyzing the reasons, it may be: The chemical modification process of tetrafluoroethylene monomer grafted onto the main chain of terpene resin under the initiation of benzoyl peroxide significantly improves the weather resistance, abrasion resistance and anti-fouling properties of terpene resin. The introduction of tetrafluoroethylene gives the resin surface a lower surface energy, making it more hydrophobic and anti-fouling. The modified terpene resin can better resist the erosion of materials in harsh outdoor environments such as ultraviolet rays, high temperature, and humidity, and maintain long-term stability. The addition of wear-resistant oily PAA resin further enhances the wear resistance of the binder, making it less likely to be worn or scratched during use. The addition of oily hydrophobic agent and the grafting modification of tetrafluoroethylene jointly enhance the anti-fouling performance of the binder, making the surface of the sign material less likely to be attached by pollutants and easy to clean. The components in the binder have good synergistic effects, which jointly improve the performance of the entire system.

[0009] Preferably, in the preparation method of the modified terpene resin, the feed ratio of the mixed solution of terpene resin, tetrafluoroethylene, benzoyl peroxide, chloroform and acetone is 1:(0.24-0.45):(0.05-0.1):(3-6) by weight.

[0010] By adopting the above technical solution: using the above optimized feed ratio, the preparation efficiency and product performance of the modified terpene resin can be significantly improved, providing strong support for the subsequent preparation of terpene resin-based binders and highly anti-fouling marking materials for photovoltaic solar panels.

[0011] Preferably, in the mixed solution of chloroform and acetone, the mass proportion of chloroform is 70-80%.

[0012] By adopting the above technical solution, it is helpful to fully carry out the grafting reaction, thereby improving the performance of the modified terpene resin.

[0013] Preferably, the polyester film PMMA is obtained by modifying MMA monomer with polycarbonate diol, and its preparation method comprises: A1. Mix MMA monomer and polycarbonate diol evenly and add them into a polymerization kettle, then add initiator and keep the temperature at 60-65℃ for reaction for 0.3-0.5h; A2, monitor the reaction degree, stop heating when it reaches the predetermined value, and proceed to the next step; A3. The block or flake product obtained by polymerization is crushed and granulated, and the granulated product is dried to remove residual moisture and solvent, and then melt-extruded and cast to obtain a polyester film PMMA.

[0014] By adopting the above technical scheme: polycarbonate diol, as a polyol, has excellent weather resistance, heat resistance and mechanical properties. By introducing it into the polymerization system of MMA, the performance of PMMA can be improved by chemical bonding, especially in terms of anti-fouling and weather resistance. The anti-fouling, weather resistance and mechanical strength of polyester film PMMA are improved. The whole preparation process has strong controllability, and the performance of the product can be optimized by adjusting the raw material ratio, reaction conditions and post-processing parameters.

[0015] Preferably, the polycarbonate diol has a viscosity of 5000-15000 mPa·s and a number average molecular weight of 800.

[0016] By adopting the above technical solution: selecting polycarbonate diol with a viscosity of 5000-15000 mPa·s and a number average molecular weight of 800 as a modifier, it is helpful to prepare a polyester film PMMA with excellent performance, which meets the high requirements of identification materials for photovoltaic solar panels.

[0017] Preferably, the feed ratio of the MMA monomer, the polycarbonate diol and the initiator is 1:(0.31-0.36):(0.15-0.17) by weight.

[0018] By adopting the above technical solution: an appropriate feed ratio helps to obtain a polymerization system with good processing performance. During the melt extrusion and cast molding process, the evenly mixed materials can flow and form more smoothly, reducing blockage and breakage in the production process.

[0019] In the second aspect, the present application provides a method for preparing a highly anti-fouling photovoltaic solar panel marking material using the following technical solution: A method for preparing a highly anti-fouling photovoltaic solar panel marking material comprises the following steps: S1. Preparation of terpene resin-based binder: add ethyl ester and wear-resistant oily PAA resin to a reaction vessel, stir at a uniform speed for 30-35 min at 80-120° C., then add modified terpene resin, cool to 70-75° C., continue stirring for 2-3 h, and when cooled to 55-60° C., continue to add oily antioxidant, ethylene glycol leveling agent, oily silicone defoamer, photoinitiator, ethyl ester, oily hydrophobic agent, stir at a uniform speed for 0.5-1 h to obtain; S2, coating and laminating: firstly coat maleic acid ester on the surface of the polyester film PMMA, then coat the terpene resin-based binder to make it fully adhered, and then laminat the environmentally friendly isolation paper thereon, so as to obtain the marking material for photovoltaic solar panels with high anti-fouling property.

[0020] By adopting the above technical scheme: the preparation method has a high anti-fouling photovoltaic solar panel marking material with excellent comprehensive performance through reasonable raw material selection and ratio, as well as precise preparation process control. During the preparation of the terpene resin-based binder, the various components work synergistically to jointly improve the anti-fouling, wear resistance, weather resistance and adhesion of the marking material; The coating and lamination process is simple and efficient, which can ensure the close bonding between the marking material and the polyester film while keeping the surface flat and smooth. The use of environmentally friendly isolation paper not only protects the surface of the binder, but also meets environmental protection requirements and reduces pollution during production and use.

[0021] Preferably, the coating thickness of the maleate is 5-6U.

[0022] By adopting the above technical solution: maleic acid ester is used as a primer or tackifier, and its main function is to enhance the adhesion between the subsequently coated terpene resin-based binder and the polyester film PMMA. The thickness of 5-6U is sufficient to form a uniform film, which effectively improves the interaction between the interfaces and thus enhances the overall adhesion effect.

[0023] In summary, the present application has at least one of the following beneficial effects: 1. By using modified terpene resin as the main component of the binder and introducing a variety of functional additives such as wear-resistant oily PAA resin, oily antioxidant, oily silicone defoamer and oily hydrophobic agent, the weather resistance of the sign material is significantly improved. The modified terpene resin enhances its weather resistance and chemical stability, while the polycarbonate diol modification of the polyester film PMMA further improves the anti-fouling performance of the material. With the combined effect of these measures, the sign material can be used for a long time in harsh outdoor environments without being easily contaminated and damaged; 2. During the preparation process, the preparation quality of the terpene resin-based binder and the polyester film PMMA is ensured by precisely controlling the feed ratio of the raw materials and the reaction conditions. In the coating and laminating step, a layer of maleate is first coated on the surface of the polyester film PMMA as a primer, and then the terpene resin-based binder is coated, so that the two can be fully bonded and tightly combined. This coating process not only simplifies the operation process, but also improves the adhesion between the marking material and the photovoltaic solar panel, ensuring that the marking material is not easy to fall off or warp during use; 3. The preparation method provided in this application takes environmental protection and cost-effectiveness into consideration in terms of raw material selection and process design. The raw materials used are all environmentally friendly materials, and the emission of harmful substances is strictly controlled during the preparation process. At the same time, by optimizing the feed ratio and reaction conditions, the utilization rate of raw materials and the yield rate of products are improved, and the production cost is reduced. In addition, the use of environmentally friendly isolation paper not only protects the surface of the binder from pollution and damage, but also facilitates subsequent installation and maintenance work, further improving the use value and economic benefits of the product. DETAILED DESCRIPTION

[0024] The present application is further described in detail below in conjunction with the examples. Except for the special instructions below, the raw materials used in the present application are all common commercially available materials.

[0025] Preparation Example 1 A modified terpene resin, the raw materials and the corresponding amounts (kg) are shown in the following table.

[0026] The preparation method of the modified terpene resin comprises the following steps: S1. Dispersing the terpene resin in a mixed solution of chloroform and acetone, wherein the mass proportion of chloroform is 80%, and then, in a nitrogen atmosphere, adding tetrafluoroethylene monomer and benzoyl peroxide to the mixed solution, and mixing them evenly; S2. Control the reaction temperature to 25-50 degrees Celsius. After reacting for 5-15 minutes, the tetrafluoroethylene monomer is grafted onto the main chain of the terpene resin under the action of benzoyl peroxide to obtain a modified terpene resin.

[0027] In the preparation example of the present application, the terpene resin brand is T-100, the softening point (°C) is 105±5°C, and the acid value (mgKOH / g): ≤1.0mgKOH / g.

[0028] Preparation Example 2-5 A modified terpene resin is different from Preparation Example 1 in that the raw material components and their corresponding weights are shown in the following table.

[0029] Example 1 A highly anti-fouling marking material for photovoltaic solar panels, comprising a polyester film PMMA and an environmentally friendly isolation paper, wherein the polyester film PMMA is bonded to the environmentally friendly isolation paper via a terpene resin-based binder; The above-mentioned terpene resin-based binder, raw materials and corresponding amounts (kg) are shown in the following table.

[0030] The method for preparing the above-mentioned highly anti-fouling photovoltaic solar panel marking material comprises the following steps: S1. Preparation of terpene resin-based binder: Add ethyl ester and wear-resistant oily PAA resin to a reaction vessel, stir at a uniform speed for 30-35 min at 80-120° C., then add the modified terpene resin prepared in Preparation Example 1, cool to 70-75° C., continue stirring for 2-3 h, and when cooled to 55-60° C., continue to add oily antioxidant, ethylene glycol leveling agent, oily silicone defoamer, photoinitiator, ethyl ester, oily hydrophobic agent, stir at a uniform speed for 0.5-1 h to obtain; S2, coating and laminating: firstly coat the surface of the polyester film PMMA with a thickness of 5-6U maleic acid ester, then coat the terpene resin-based binder to make it fully adhered, and then laminarize the environmentally friendly isolation paper thereon to obtain a highly anti-fouling photovoltaic solar panel marking material.

[0031] The polyester film PMMA is obtained by modifying MMA monomer with polycarbonate diol, and its preparation method comprises: A1, mixing MMA monomer and polycarbonate diol uniformly and adding them into a polymerization kettle, then adding an initiator, and keeping the temperature at 60-65° C. for reaction for 0.3-0.5 h; A2, monitor the reaction degree, stop heating when it reaches the predetermined value, and proceed to the next step; A3. The block or flake product obtained by polymerization is crushed and granulated, and the granulated product is dried to remove residual moisture and solvent, and then melt-extruded and cast to obtain a polyester film PMMA.

[0032] The viscosity of polycarbonate diol is 8500 mPa·s and the number average molecular weight is 800; The raw materials and their corresponding dosage (kg) are shown in the following table. raw material Dosage MMA monomer 1 Polycarbonate diol 0.32 Initiator 0.16

[0033] Example 2-3 A highly anti-fouling marking material for photovoltaic solar panels, which is different from Example 1 in that the above-mentioned terpene resin-based binder, various raw materials and corresponding amounts (kg) are shown in the following table.

[0034] Embodiment 4-7 A highly anti-fouling marking material for photovoltaic solar panels, which is different from Example 1 in that the modified terpene resin is prepared by different preparation examples, and the specific details are shown in the table below. Example Modified terpene resin source Example 4 Prepared from Preparation Example 2 Example 5 Prepared from Preparation Example 3 Example 6 Prepared by Preparation Example 4 Example 7 Prepared from Preparation Example 5

[0035] Embodiment 8-11 A highly anti-fouling marking material for photovoltaic solar panels is different from Example 1 in that different amounts of PMMA raw materials are used to prepare the polyester film. The raw materials and their corresponding amounts (kg) are shown in the following table.

[0036] Example 12 A highly anti-fouling marking material for photovoltaic solar panels, which is different from Example 1 in that the polycarbonate diol is selected from Mitsubishi HS0850H of Japan, has a viscosity of 15000 mPa·s, and a number average molecular weight of 800.

[0037] Comparative Example 1 A highly anti-fouling marking material for photovoltaic solar panels, which is different from Example 1 in that: The polyester film PMMA in the raw material for preparing the marking material for the highly anti-fouling photovoltaic solar panel is replaced by the common film PMMA, that is, the PMMA is not modified.

[0038] Comparative Example 2 A highly anti-fouling marking material for photovoltaic solar panels, which is different from Example 1 in that: The terpene resin in the terpene resin-based binder, which is one of the raw materials for preparing the marking material for the photovoltaic solar panel with high anti-fouling property, is not modified, that is, ordinary terpene resin is used to replace the modified terpene resin.

[0039] Performance testing 1. Anti-fouling performance test First, cut a sample of a certain area (e.g. 10cm x 10cm) from the marking material for the photovoltaic solar panel to be tested, ensure that the surface of the sample is flat and scratch-free, and try to simulate the actual use state; According to the actual application scenario, prepare a series of common pollutants, including fine dust or sand (simulating dust and sand in the natural environment), wet soil (simulating pollution after rain), cooking oil or motor oil (simulating grease pollution), and water stains of clean water or simulated rain (to evaluate the material's ability to absorb and repel water); Use a spray bottle to evenly apply the prepared contaminant on the sample surface, ensuring that the contaminant covers the entire test area and simulating the degree and method of contamination that may be encountered in actual use. After the sample with the contaminant is placed at room temperature for 72 hours, carefully observe the adhesion of the contaminant on the material surface, and record the adhesion amount (area percentage), distribution state (whether there is aggregation), and adhesion strength (whether it is easy to peel off with fingers or tools).

[0040] 2. Weathering test The photovoltaic solar panel marking material to be tested was placed in a comprehensive test box simulating a desert environment. Taking into account the combined effects of ultraviolet rays, high temperature, wind and sand, the test was carried out at 60°C, 1.32W / m 2 The material was tested continuously for 90 days under the specified conditions to evaluate its overall weather resistance in the desert environment, and its wear resistance was evaluated according to the GB / T 1768 standard ≤0.05g.

[0041] The photovoltaic solar panel marking materials prepared in Examples 1-13 and Comparative Examples 1-2 of the present application were subjected to relevant performance tests according to the above-mentioned test methods, and the results are shown in the table below.

[0042] Through the data analysis of the above table, it can be seen that the highly anti-fouling photovoltaic solar panel marking materials prepared in Examples 1-5 have excellent anti-fouling performance and weather resistance, wherein the amount of stains attached is less than 15%, and there is no aggregation phenomenon, and they can be peeled off by wiping with hands; the wear resistance is ≤0.05g, and there is no peeling, fading, or deformation; The highly anti-fouling photovoltaic solar panel marking materials prepared in Examples 6-7 performed well in terms of anti-fouling performance, but their weather resistance decreased and they all showed deformation. This may be because the excessive initiator benzoyl peroxide introduced more free radicals, which may cause further degradation reactions when exposed to light, high temperature and other conditions for a long time, thereby affecting the weather resistance of the material.

[0043] Among Examples 8-11, only the highly anti-fouling photovoltaic solar panel marking material prepared in Example 8 had a stain attachment amount exceeding 15%, and slight aggregation and fading occurred.

[0044] In Example 8, the amount of polycarbonate diol increased from 0.32 kg to 0.36 kg. This increase may change the molecular chain length of the polyester film PMMA, thereby affecting its surface properties. Too much polycarbonate diol may cause changes in the surface energy of the film, making it more susceptible to adsorbing stains or aggregation. It may also affect the crystallinity and phase separation behavior of the polyester film, thereby affecting its optical properties and weather resistance, leading to fading.

[0045] The highly anti-fouling marking materials for photovoltaic solar panels prepared in Example 12 and Comparative Examples 1-2 performed poorly in terms of anti-fouling performance and weather resistance, with the stain attachment amount being greater than 15%, and stain aggregation to varying degrees. The stain attachment amount in Comparative Example 1 even reached 44%, and the stain attachment strength was also greatly enhanced; in terms of weather resistance, the wear resistance was greater than 0.05g, and peeling, fading, and deformation to varying degrees occurred; In Example 12, a polycarbonate diol with a higher viscosity (Japan Mitsubishi HS0850H, with a viscosity of 15000 mPa·s) was selected, which may lead to enhanced interactions between molecular chains of the polyester film PMMA and changes in surface energy, thereby affecting its anti-fouling performance. The high viscosity may make the film surface more susceptible to stains and difficult to clean; In Comparative Example 1, an ordinary PMMA film that is not modified with polycarbonate diol is used. The surface properties of the ordinary PMMA film may not be conducive to anti-fouling, and its weather resistance is poor, and it is easily affected by the external environment and fades and deforms; Unmodified common terpene resin was used as part of the binder in Comparative Example 2. The modified terpene resin may have better adhesion, weather resistance and stain resistance, while the common terpene resin may not perform well in these aspects, resulting in reduced performance of the final product.

[0046] The above are all modifications without creative contribution or solutions that obviously constitute technical inspiration that can be made to the present embodiment as needed by technical personnel in this field after reading this specification, but they should be protected by patent law as long as they are within the scope of the claims of this application.

Claims

1. A highly anti-fouling marking material for photovoltaic solar panels, characterized in that: It includes a polyester film PMMA and an environmentally friendly isolation paper, wherein the polyester film PMMA is bonded to the environmentally friendly isolation paper via a terpene resin-based adhesive; The raw materials for preparing the terpene resin-based binder include the following components by weight percentage: Modified terpene resin 32-36% Wear-resistant oily PAA resin 10-12% Oily antioxidant 2-3% Ethylene glycol leveling agent 2-3% Oily silicone defoamer 1-2% Photoinitiator 3-4% Ethyl ester 38-40% Oily hydrophobic agent 2-3% The preparation method of the modified terpene resin comprises the following steps: S1. Dispersing the terpene resin in a mixed solution of chloroform and acetone, and then adding tetrafluoroethylene monomer and benzoyl peroxide to the mixed solution under a nitrogen atmosphere, and mixing them evenly; S2. Control the reaction temperature to 25-50 degrees Celsius. After reacting for 5-15 minutes, the tetrafluoroethylene monomer is grafted onto the main chain of the terpene resin under the action of benzoyl peroxide to obtain a modified terpene resin.

2. The highly anti-fouling marking material for photovoltaic solar panels according to claim 1, characterized in that: In the preparation method of the modified terpene resin, the feeding ratio of the mixed solution of terpene resin, tetrafluoroethylene, benzoyl peroxide, chloroform and acetone is 1: (0.24-0.45): (0.05-0.1): (3-6) by weight.

3. The highly anti-fouling marking material for photovoltaic solar panels according to claim 1, characterized in that: In the mixed solution of chloroform and acetone, the mass proportion of chloroform is 70-80%.

4. The highly anti-fouling marking material for photovoltaic solar panels according to claim 1, characterized in that: The polyester film PMMA is obtained by modifying MMA monomer with polycarbonate diol, and its preparation method comprises: A1. Mix MMA monomer and polycarbonate diol evenly and add them into a polymerization kettle, then add initiator and keep the temperature at 60-65℃ for reaction for 0.3-0.5h; A2, monitor the reaction degree, stop heating when it reaches the predetermined value, and proceed to the next step; A3. The block or flake product obtained by polymerization is crushed and granulated, and the granulated product is dried to remove residual moisture and solvent, and then melt-extruded and cast to obtain a polyester film PMMA.

5. The highly anti-fouling marking material for photovoltaic solar panels according to claim 4, characterized in that: The viscosity of the polycarbonate diol is 5000-15000 mPa·s, and the number average molecular weight is 800.

6. The highly anti-fouling marking material for photovoltaic solar panels according to claim 4, characterized in that: The feed ratio of the MMA monomer, the polycarbonate diol and the initiator is 1:(0.31-0.36):(0.15-0.17) by weight.

7. A method for preparing a highly anti-fouling marking material for photovoltaic solar panels, characterized in that: The method comprises the following preparation steps: S1. Preparation of terpene resin-based binder: add ethyl ester and wear-resistant oily PAA resin to a reaction vessel, stir at a uniform speed for 30-35 min at 80-120° C., then add modified terpene resin, cool to 70-75° C., continue stirring for 2-3 h, and when cooled to 55-60° C., continue to add oily antioxidant, ethylene glycol leveling agent, oily silicone defoamer, photoinitiator, ethyl ester, oily hydrophobic agent, stir at a uniform speed for 0.5-1 h to obtain; S2, coating and laminating: firstly coat maleic acid ester on the surface of the polyester film PMMA, then coat the terpene resin-based binder to make it fully adhered, and then laminat the environmentally friendly isolation paper thereon, so as to obtain the marking material for photovoltaic solar panels with high anti-fouling property.

8. The method for preparing a highly anti-fouling photovoltaic solar panel marking material according to claim 7, characterized in that: The coating thickness of the maleate is 5-6U.

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